CN109311917B - Process for preparing alkoxysilanes - Google Patents
Process for preparing alkoxysilanes Download PDFInfo
- Publication number
- CN109311917B CN109311917B CN201780036003.2A CN201780036003A CN109311917B CN 109311917 B CN109311917 B CN 109311917B CN 201780036003 A CN201780036003 A CN 201780036003A CN 109311917 B CN109311917 B CN 109311917B
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- group
- alkoxysilane
- transesterification
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 157
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 239000012429 reaction media Substances 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 131
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 63
- 239000007795 chemical reaction product Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 47
- -1 glycidyloxy Chemical group 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 21
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 229910052757 nitrogen Chemical group 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000006227 byproduct Substances 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Chemical group 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 239000000126 substance Chemical group 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 125000004419 alkynylene group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 125000005724 cycloalkenylene group Chemical group 0.000 claims description 3
- 238000010908 decantation Methods 0.000 claims description 3
- 239000000413 hydrolysate Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- MOWSUOKIHAQPCR-UHFFFAOYSA-N diethoxy-ethyl-[1-(7-oxabicyclo[4.1.0]heptan-4-yl)ethoxy]silane Chemical compound C1C(C(C)O[Si](CC)(OCC)OCC)CCC2OC21 MOWSUOKIHAQPCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 108010009736 Protein Hydrolysates Proteins 0.000 claims 1
- 229910021485 fumed silica Inorganic materials 0.000 claims 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000010936 titanium Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000000526 short-path distillation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 238000000998 batch distillation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- DAJFVZRDKCROQC-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tripropoxysilane Chemical compound CCCO[Si](OCCC)(OCCC)CCCOCC1CO1 DAJFVZRDKCROQC-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Chemical group 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- MXDWUGFTSGOHRF-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propylurea Chemical compound CO[Si](C)(OC)CCCNC(N)=O MXDWUGFTSGOHRF-UHFFFAOYSA-N 0.000 description 1
- DQMRXALBJIVORP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(C)CCCS DQMRXALBJIVORP-UHFFFAOYSA-N 0.000 description 1
- JOFFHZWPDCZGQK-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propylurea Chemical compound CO[Si](C)(C)CCCNC(N)=O JOFFHZWPDCZGQK-UHFFFAOYSA-N 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- PLXLQGPXPXIVKM-UHFFFAOYSA-N 3-chloropropyl(tripropoxy)silane Chemical compound CCCO[Si](CCCCl)(OCCC)OCCC PLXLQGPXPXIVKM-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- JTWDWVCNOLORBR-UHFFFAOYSA-N 3-chloropropyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)CCCCl JTWDWVCNOLORBR-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- DECHJJJXDGPZHY-UHFFFAOYSA-N 3-tripropoxysilylpropane-1-thiol Chemical compound CCCO[Si](CCCS)(OCCC)OCCC DECHJJJXDGPZHY-UHFFFAOYSA-N 0.000 description 1
- JYJOAXGGEJCHOW-UHFFFAOYSA-N 3-tripropoxysilylpropylurea Chemical compound CCCO[Si](OCCC)(OCCC)CCCNC(N)=O JYJOAXGGEJCHOW-UHFFFAOYSA-N 0.000 description 1
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- PGQPMLCDSAVZNJ-BGSQTJHASA-L [dimethyl-[(z)-octadec-9-enoyl]oxystannyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCCC\C=C/CCCCCCCC PGQPMLCDSAVZNJ-BGSQTJHASA-L 0.000 description 1
- NNVDGGDSRRQJMV-UHFFFAOYSA-L [dioctyl(2,2,5,5-tetramethylhexanoyloxy)stannyl] 2,2,5,5-tetramethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(C)(C)CCC(C)(C)C)(OC(=O)C(C)(C)CCC(C)(C)C)CCCCCCCC NNVDGGDSRRQJMV-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- GNRBSDIBKIHSJH-UHFFFAOYSA-N butyl(tripropoxy)silane Chemical compound CCCC[Si](OCCC)(OCCC)OCCC GNRBSDIBKIHSJH-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- OJJSYTLVICNTMF-UHFFFAOYSA-H dibismuth 2,2,3,3-tetramethylheptanedioate Chemical compound [Bi+3].[Bi+3].CC(C)(CCCC([O-])=O)C(C)(C)C([O-])=O.CC(C)(CCCC([O-])=O)C(C)(C)C([O-])=O.CC(C)(CCCC([O-])=O)C(C)(C)C([O-])=O OJJSYTLVICNTMF-UHFFFAOYSA-H 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- GOIPELYWYGMEFQ-UHFFFAOYSA-N dimethoxy-methyl-octylsilane Chemical compound CCCCCCCC[Si](C)(OC)OC GOIPELYWYGMEFQ-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- GGSRSEXZHCIQEF-UHFFFAOYSA-N ethyl-[1-(7-oxabicyclo[4.1.0]heptan-4-yl)propoxy]-dipropoxysilane Chemical compound C1C(C(CC)O[Si](CC)(OCCC)OCCC)CCC2OC21 GGSRSEXZHCIQEF-UHFFFAOYSA-N 0.000 description 1
- PPTRWDPXGSVIER-UHFFFAOYSA-N ethyl-dimethyl-(7-oxabicyclo[4.1.0]heptan-3-ylmethoxy)silane Chemical compound C1(CC2C(CC1)O2)CO[Si](C)(C)CC PPTRWDPXGSVIER-UHFFFAOYSA-N 0.000 description 1
- RFUMPKRQUVFNPF-UHFFFAOYSA-N ethyl-methoxy-methyl-(7-oxabicyclo[4.1.0]heptan-3-ylmethoxy)silane Chemical compound O1C2CC(CCC21)CO[Si](OC)(C)CC RFUMPKRQUVFNPF-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- IAGREDBVCFAKQR-UHFFFAOYSA-N hexyl(tripropoxy)silane Chemical compound CCCCCC[Si](OCCC)(OCCC)OCCC IAGREDBVCFAKQR-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- FBNXYLDLGARYKQ-UHFFFAOYSA-N methoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(C)CCCOCC1CO1 FBNXYLDLGARYKQ-UHFFFAOYSA-N 0.000 description 1
- BAXHQTUUOKMMGV-UHFFFAOYSA-N methoxy-dimethyl-octylsilane Chemical compound CCCCCCCC[Si](C)(C)OC BAXHQTUUOKMMGV-UHFFFAOYSA-N 0.000 description 1
- NCHMPORHGFKNSI-UHFFFAOYSA-N methoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OC NCHMPORHGFKNSI-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A transesterification process for preparing alkoxysilanes comprising removing a metal transesterification catalyst from an alkoxysilane transesterification reaction medium.
Description
Cross Reference to Related Applications
This application claims priority to provisional U.S. patent application serial No. 62/348,436, filed 2016, month 6 and day 10, which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to a catalyzed transesterification process for the preparation of alkoxysilanes.
Background
The alkoxysilane may be prepared by: transesterifying a transesterifiable alkoxysilane (reactant) and an alcohol in the presence of a metal transesterification catalyst to produce a transesterified reaction product in which at least one alkoxy group of the transesterifiable alkoxysilane is transesterified with an alkoxy group of an esterified alcohol. As the transesterification reaction proceeds, the byproduct alcohol produced in the transesterification reaction is often removed from the reaction medium to drive the reaction to completion. In the aforementioned transesterification process, the transesterification catalyst may be separated from the transesterification reaction product of the alkoxysilane by distillation, or the catalyst may remain in the transesterification reaction product of the alkoxysilane. Indeed, for some applications, the presence of a metal transesterification catalyst in the alkoxysilane reaction product may be desirable.
In the foregoing processes for preparing the transesterification reaction product of the alkoxysilane, the metal transesterification catalyst that may be present in the alkoxysilane reaction product may lead to the formation of siloxanes, especially during normal or expected periods of storage, e.g., durations of 1 month to 4 years. The formation of the siloxane can negatively affect the product purity even to the extent that the product is unacceptable for use.
In some cases, the retained metal transesterification catalyst may precipitate out of solution to interfere with subsequent processing, such as pumping from a storage device (storage) during downstream manufacturing operations.
The metal transesterification catalyst may have a boiling point similar to or form an azeotrope with the alkoxysilane reaction product. In these cases, the catalyst and product can be co-distilled and thus the metal transesterification catalyst is not effectively removed from the transesterification reaction product of the alkoxysilane. The co-distillation of the transesterification reaction product of the catalyst and the alkoxysilane after the transesterification reaction is complete can also interfere with the normal operation of the condenser, particularly caused by the build-up of solids therein. Moreover, as noted above, the presence of a catalyst in the transesterification reaction product of the alkoxysilane may result in the formation of siloxane or precipitation out of solution.
It will also be noted that the presence of the metal transesterification catalyst in the transesterification reaction product of the alkoxysilane may result in undesirable chemical reactions occurring or accelerate hydrolysis and condensation reaction products of the transesterification reaction product of the alkoxysilane. These reactions depend on the nature of the transesterification reaction product of the alkoxysilane and the particular use to which the product is put, since, for example, the reaction of an epoxide with an amine, the formation of a siloxane, or the crosslinking of a silylated polymer can shorten the shelf life of the end-use product.
Therefore, there is a need for a method for removing some or substantially all of the metal transesterification catalyst from the transesterification reaction product of the alkoxysilane, thereby eliminating any interference with the normal operation of the condenser during distillation or other separation processes.
Disclosure of Invention
In accordance with the present invention, there is provided a process for preparing a transesterification reaction product of an alkoxysilane comprising transesterifying at least one transesterifiable alkoxysilane and at least one alcohol in the presence of at least one metal transesterification catalyst under transesterification reaction conditions, optionally accompanied by removal of by-product alcohol and/or unreacted alcohol, to produce a transesterification reaction product of the alkoxysilane, followed by removal of at least a portion of the catalyst from the reaction product.
The removal of the metal transesterification catalyst from the transesterification reaction product of the alkoxysilane is achieved by: (i) hydrolyzing the catalyst to form a metal oxide precipitate and then subsequently filtering to remove the metal oxide precipitate, or (ii) adsorbing the metal transesterification catalyst onto a suitable adsorption medium.
In accordance with the present invention, the aforementioned problems of gelation, catalyst precipitation, condenser failure and undesirable chemical reactions are alleviated by removing at least a substantial portion of the metal transesterification catalyst remaining in the transesterification reaction product of the alkoxysilane after the transesterification is complete, or are largely or even completely eliminated in the event that the catalyst is substantially completely separated from the reaction product, for example, at least about 80 percent, more preferably at least about 90 percent, and more preferably at least about 95 percent by weight of the catalyst is separated from the reaction product.
Detailed Description
In the description and claims herein, the following terms and expressions should be understood as being descriptive.
The singular forms "a", "an" and "the" encompass the plural, and reference to a particular numerical value includes at least that value, unless the context clearly dictates otherwise.
The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed.
No language in the specification should be construed as indicating any non-limiting element as essential to the practice of the invention.
The terms "comprising," including, "" containing, "" characterized by, "and grammatical equivalents thereof are inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps, but are also to be construed to include the more limiting terms" consisting of … … "and" consisting essentially of … ….
All numerical values herein should be understood as modified by the term "about" except in the context of working examples or where a particular value is explicitly indicated as being exact.
It will be understood that any numerical range recited herein includes all sub-ranges falling within that range and any combination of the various endpoints of such ranges or sub-ranges.
It will also be understood that any compound, material or substance which is disclosed or claimed as belonging to a group of structurally, compositionally and/or functionally related compounds, materials or substances, either explicitly or implicitly in the specification and/or in the claims, includes individual representatives of the group and all combinations thereof.
The term "alkyl" means any monovalent saturated linear or branched hydrocarbon group; the term "alkenyl" means any monovalent linear or branched hydrocarbon group containing one or more carbon-carbon double bonds, wherein the site of attachment of the group may be at a carbon-carbon double bond or elsewhere therein; and, the term "alkynyl" means any monovalent linear or branched hydrocarbon group containing one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds, wherein the site of attachment of the group may be at a carbon-carbon triple bond, a carbon-carbon double bond, or elsewhere therein. Examples of alkyl groups include methyl, ethyl, propyl, and isobutyl. Examples of alkenyl groups include vinyl, propenyl, allyl or methallyl. Examples of alkynyl groups include ethynyl, propynyl and methylacetylenyl.
The term "cycloalkyl" means any monovalent hydrocarbon group containing a cyclic structure; the term "cycloalkenyl" means any monovalent hydrocarbon group containing a ring structure and one or more carbon-carbon double bonds, where the site of attachment of the group can be at or elsewhere in the carbon-carbon double bond; and, the term "cycloalkynyl" means any monovalent hydrocarbon group containing a ring structure and one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds, wherein the site of attachment of the group may be at a carbon-carbon triple bond, a carbon-carbon double bond, or elsewhere therein. The expressions "cycloalkyl", "cycloalkenyl" and "cycloalkynyl" include monocyclic, bicyclic, tricyclic, and higher cyclic structures as well as the aforementioned cyclic structures further substituted with alkyl, alkenyl, and/or alkynyl groups. Representative examples include norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, cyclododecatrienyl, ethylidenenorbornyl, ethylidenenorbornene and ethylidenenorbornenyl.
The term "aryl" means any monovalent aromatic hydrocarbon group; the term "aralkyl" means any alkyl group (as defined herein) in which one or more hydrogen atoms have been substituted by the same number of the same and/or different aryl (as defined herein) groups; and, the term "alkaryl" means any aryl group (as defined herein) in which one or more hydrogen atoms have been replaced by the same number of identical and/or different alkyl groups (as defined herein). Examples of aryl groups include phenyl and naphthyl. Examples of aralkyl groups include benzyl and phenethyl. Examples of alkaryl groups include tolyl and xylyl.
The expression "transesterification reaction medium" is understood herein to include a medium which, when formed, is present at any particular time during the transesterification and is present after the transesterification is complete.
The expression "transesterification reaction product of an alkoxysilane" as used herein is to be understood as including transesterification reaction products of monomeric, dimeric or oligomeric alkoxysilanes and in the case of transesterification reaction products of dimeric and oligomeric alkoxysilanes possesses a dialkoxy bridging group connecting adjacent silane units.
In one embodiment of the invention, the transesterification reaction products of alkoxysilanes and mixtures thereof may be obtained by reacting one or more transesterifiable alkoxysilanes of formula (I) with one or more transesterifiable alcohols of formula (II) under catalytic transesterification conditions, optionally with the concomitant removal of by-products and/or unreacted alcohols, in the presence of a catalytically effective amount of one or more metal transesterification catalysts of formula (III):
Y-[R1-Si(R2)3-a(OR3)a]b (I)
wherein:
y is hydrogen, halogen or a functional group;
each R1Independently is a divalent linear alkylene group of 1 to 12 carbon atoms, a branched alkylene group of 2 to 12 carbon atoms, a cycloalkylene group of 3 to 12 carbon atoms, an arylene group of 6 to 10 carbon atoms, an aralkyl group of 7 to 16 carbon atoms, an alkenylene group of 2 to 12 carbon atoms, a cycloalkenylene group of 3 to 12 carbon atoms, an alkynylene group of 2 to 12 carbon atoms, a linear alkylene, branched alkylene or cycloalkylene group containing at least one heteroatom selected from sulfur, oxygen or nitrogen and 2 to 12 carbon atoms, or a chemical bond, with the proviso that in R1Y is an organic functional group in which a silicon atom is bonded to a carbon atom of the group Y in the case of a chemical bond;
each R2Independently a monovalent straight chain alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 16 carbon atoms;
each R3Independently a monovalent straight chain alkyl of 1 to 4 carbon atoms or a branched alkyl of 3 to 4 carbon atoms;
a is an integer of 1 to 3; and the combination of (a) and (b),
b is an integer of 1 to 4,
R4OH (II)
wherein:
R4is monovalent of 1 to 16 carbon atomsA linear alkyl radical, a branched alkyl radical of 3 to 16 carbon atoms, a cycloalkyl radical of 3 to 12 carbon atoms, an alkenyl radical of 2 to 16 carbon atoms, an aralkyl radical of 7 to 12 carbon atoms, an aryl radical of 6 to 10 carbon atoms, a linear alkyl radical comprising 2 to 16 carbon atoms containing at least one heteroatom selected from oxygen, sulphur or nitrogen or a branched alkyl radical comprising 3 to 16 carbon atoms containing at least one heteroatom selected from oxygen, sulphur or nitrogen, a branched alkyl radical of 2 to 16 carbon atoms and being substituted by-NR-at least on the hydroxyl or amino group5R6Substituted linear or branched alkyl, wherein R5And R6Independently hydrogen, or a straight chain alkyl group of 1 to 16 carbon atoms, a branched alkyl group of 3 to 16 carbon atoms, an aryl group of 6 to 10 carbon atoms or an aralkyl group of 7 to 12 carbon atoms,
Mn+(X)n (III)
wherein:
m is a metal that is catalytically active for transesterification;
x is OR7Or X is R8Provided that at least one X is OR7Wherein each R7Independently a monovalent straight chain alkyl group of 1 to 12 carbon atoms, a branched alkyl group of 3 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an aryl group of 6 to 10 carbon atoms, an aralkyl group of 9 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, an acyl group of 1 to 12 carbon atoms, OR two OR' s7The radicals being bonded to one another via carbon-carbon bonds to form-O-R7-R7-O-group, wherein R8Is a monovalent straight chain alkyl group of 1 to 16 carbon atoms, a branched alkyl group of 3 to 16 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an aryl group of 6 to 10 carbon atoms or an aralkyl group of 7 to 12 carbon atoms; and the combination of (a) and (b),
n is the valence of M.
In the transesterifiable alkoxysilanes (I), the individual alkoxy groups OR3Independently preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxy, and more preferably methoxy, ethoxy or propoxy, a is preferably 2 or 3, and more preferably 3, b is preferably 1, and Y is preferably hydrogen, halogen, mercapto, glycidoxy, epoxycyclohexyl, ureido, carbamoyl, acryloyloxy, methacryloyloxyAcyloxy, amino, or vinyl.
Specific transesterifiable alkoxysilanes (I) which may be subjected to transesterification herein include, but are not limited to, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltripropoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-glycidoxypropyltrimethoxysilane, tert-butyl-triethoxysilane, tert-butyl-ethyl-butyl-n-butyl-triethoxysilane, tert-butyl-tri-propyl-butyl-ethyl-butyl-trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltripropoxysilane, (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (3, 4-epoxycyclohexyl) ethyltripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, propylmethyldimethoxysilane, propyldimethylmethoxysilane, octylmethyldimethoxysilane, octyldimethylmethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidol, and/2-triethoxysilane, and/2-methyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-ureidopropylmethyldimethoxysilane, 3-ureidopropyldimethylmethoxysilane, (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, (3, 4-epoxycyclohexyl) ethyldimethylmethoxysilane, vinylmethyldimethoxysilane and vinyldimethylmethoxysilane.
In the transesterified alcohol (II), R4Monovalent linear or branched alkyl groups are preferred. Thus, for example, in esterifiable estersOR in exchanged alkoxysilanes (I)3R of the alcohol (II) in the case of a methoxy group4Preferably ethyl OR higher alkyl, at OR3In the case of ethoxy, R of the alcohol (II)4Preferably propyl, isopropyl, or an alkyl group having a higher carbon number.
Specific transesterification alcohols (II) that may be used to transesterify the alkoxysilane (I) according to the process of the present invention to provide a transesterification reaction product of the alkoxysilane include, but are not limited to, methanol, ethanol, propanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, and the like.
In the metal transesterification catalyst (III), M is preferably Ti, Zr, Bi, Zn, Sn OR a mixture thereof and each X is preferably OR7Wherein R is7Is a linear or branched alkyl group of 1 to 6 carbon atoms or an acyl group of 1 to 6 carbon atoms.
Specific metal transesterification catalysts (III) useful herein for catalyzing the transesterification reaction include, but are not limited to, alkyl titanates such as methyl-, ethyl-, propyl-, isopropyl-, butyl-, sec-butyl-, tert-butyl-, and 2-ethylhexyl titanates, alkyl zirconates such as ethyl-, propyl-, and butyl zirconates, alkyl bismuthates such as bismuth (2-ethylhexanoate), bismuth neodecanoate, and bismuth tetramethylheptanedioate, and alkyl stannates such as dibutyltin dilaurate, dioctyltin dineodecanoate, and dimethyltin dioleate.
The metal transesterification catalyst (III) will be present in the transesterification reaction medium in at least a catalytically effective amount. The amount of catalyst can vary widely, for example, from about 0.01 weight percent to about 5 weight percent in one embodiment, from about 0.1 weight percent to about 3 weight percent in another embodiment, and from about 0.5 weight percent to about 2 weight percent in yet another embodiment, based on the total weight of the transesterifiable alkoxysilane (I).
The catalytic transesterification reaction conditions include those known to those of ordinary skill in the art and may vary widely depending on the catalyst concentration, the nature and amount of the metal transesterification catalyst (III), the transesterifiable alcohol (II), and the transesterifiable alkoxysilane (I). Typically and as is well known in the art, the transesterification reaction will be carried out at a temperature and pressure range in which by-products and/or unreacted alcohol can be recovered as the reaction proceeds. Normally, the reaction will be carried out to substantial completion, for example, up to about 80 weight percent, and more preferably up to about 90 weight percent or greater, based on the original amount of the transesterifiable alkoxysilane (I), with the degree of completion being determined by known and conventional analytical techniques such as gas chromatography and NMR.
The reaction temperature is advantageously maintained below the boiling point of the transesterified alcohol (II) at the chosen pressure of the transesterification reaction. A fractionation column may be used to aid in the removal of the by-product alcohol. By-products are removed from the reaction medium during the transesterification in order to drive the reaction to completion. Typical transesterification reaction conditions include a temperature from room temperature to about 120 ℃, more preferably from about 50 ℃ to about 100 ℃ and a pressure in the range of about 0.0007 bar to about 2 bar, more preferably about 0.02 bar to about 1 bar.
After the transesterification reaction, the metal transesterification catalyst (III) is removed to a partial or substantially complete extent. In one embodiment, the removal technique comprises subjecting the catalyst to hydrolysis followed by filtration to remove metal oxide precipitates formed by the hydrolysis reaction, or adsorbing the catalyst on a suitable adsorption medium. Generally, such techniques and combinations thereof will be used to remove at least a significant amount of the metal transesterification catalyst from the final alkoxysilane transesterification reaction product, for example, to reduce the amount of residual metal transesterification catalyst to less than about 100ppm, preferably less than about 50ppm, and more preferably less than about 10ppm, based on the weight of the alkoxysilane transesterification reaction product.
In the case of hydrolysis as a catalyst removal technique, sufficient water is added at room temperature to completely hydrolyze the metal catalyst. In one embodiment, water is generally used in an amount of about 0.1 to about 10 weight percent, and preferably about 1 to about 5 weight percent, based on the weight of the transesterification reaction product of the alkoxysilane. The reaction mixture containing the hydrolyzed metal catalyst is filtered. The filtration may be aided by the use of typical filtration aids such as diatomaceous earth. The metal oxide and a large amount or all of the water used for the hydrolysis of the catalyst are removed by filtration. The alkoxysilane may then be subjected to distillation to further purify the product, for example to remove residual water and/or by-products and/or unreacted alcohol.
In one embodiment, the hydrolysis conditions for converting the metal transesterification catalyst (III) to the metal oxide are a temperature of about 1 ℃ to about 75 ℃ and preferably about 15 ℃ to about 30 ℃, and a pressure of about 0.0007 bar to about 2 bar and preferably about 0.5 bar to about 1.2 bar.
In one embodiment, the transesterification reaction product of the alkoxysilane has the general formula (IV):
Y-[R1-Si(R2)3-a(OR3)a-c(OR4)c]b (IV)
wherein:
y is hydrogen, halogen or a functional group;
each R1Independently is a divalent linear alkylene group of 1 to 12 carbon atoms, a branched alkylene group of 2 to 12 carbon atoms, a cycloalkylene group of 3 to 12 carbon atoms, an arylene group of 6 to 10 carbon atoms, an aralkyl group of 7 to 16 carbon atoms, an alkenylene group of 2 to 12 carbon atoms, a cycloalkenylene group of 3 to 12 carbon atoms, an alkynylene group of 2 to 12 carbon atoms, a linear alkylene, branched alkylene or cycloalkylene group containing at least one heteroatom selected from sulfur, oxygen or nitrogen and 2 to 12 carbon atoms, or a chemical bond, with the proviso that in R1In the case of a chemical bond, Y is an organic functional group in which the silicon atom is bonded to a carbon atom of the group Y;
each R2Independently a monovalent straight chain alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 16 carbon atoms;
each R3Independently a monovalent straight chain alkyl of 1 to 4 carbon atoms or a branched alkyl of 3 to 4 carbon atoms;
each R4Is a monovalent straight chain alkyl group of 1 to 16 carbon atoms, of 3 to 16 carbon atomsA branched alkyl group, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 16 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, an aryl group of 6 to 10 carbon atoms, a linear alkyl group containing 2 to 16 carbon atoms containing at least one heteroatom selected from oxygen, sulfur or nitrogen or a branched alkyl group containing 3 to 16 carbon atoms containing at least one heteroatom selected from oxygen, sulfur or nitrogen, 2 to 16 carbon atoms and being substituted at least on the hydroxyl or amino group by-NR5R6Substituted linear or branched alkyl, wherein R5And R6Independently hydrogen or a straight chain alkyl group of 1 to 16 carbon atoms, a branched alkyl group of 3 to 16 carbon atoms, an aryl group of 6 to 10 carbon atoms or an aralkyl group of 7 to 12 carbon atoms
a is an integer of 1 to 3;
b is an integer of 1 to 4; and
c is an integer of 1 to 3;
provided that a and b are the values selected for the transesterifiable alkoxysilane (I) and c is selected such that a-c are 0 or positive integers.
In one embodiment, in the transesterification reaction product (IV) of the alkoxysilane, a is 3, b is 0 and c is 3.
If desired, the alkoxysilane transesterification reaction product may be blended in one embodiment with a small amount of an acid such as acetic acid or boric acid as an aid to its hydrolysis and condensation when used. In one embodiment, the acid can be used in an amount of about 1ppm to about 2 weight percent, more preferably about 50ppm to about 500ppm, based on the total weight of the transesterification reaction product of the alkoxysilane.
In the case of adsorption as the catalyst removal technique, as the adsorption medium, a solid such as fumed or precipitated silica, clay, ion exchange resin, or other particulate mineral may be used, wherein the adsorption medium may be added to adsorb the metal catalyst. When the transesterification is complete, an adsorbent media, such as precipitated silica, is added to the reaction mixture and stirred. After which filtration is carried out to remove the adsorption medium containing the metal catalyst.
In one embodiment, a process for preparing a transesterification reaction product of an alkoxysilane comprises:
(a) combining a metal transesterification catalyst, for example, in an amount of about 0.005 to about 5 weight percent, preferably about 0.01 to about 1 weight percent, based on the weight of the transesterifiable alkoxysilane, to the transesterifiable alkoxysilane to provide a mixture thereof;
(b) subjecting the mixture from step (a) to esterification reaction conditions, such as a temperature of ambient to about 120 ℃ and a pressure of about 0.0007 bar to about 2 bar, preferably about 0.02 bar to about 1 bar, while adding transesterified alcohol thereto;
(c) adding a transesterification alcohol to the mixture of metal transesterification catalyst and transesterifiable alkoxysilane prior to and/or during step (b) to provide a transesterification reaction medium, thereby initiating transesterification and producing alkoxysilane transesterification reaction product;
(d) removing from the transesterification reaction medium by-product alcohol formed during transesterification;
(e) separating the metal transesterification catalyst from the transesterification reaction medium of step (d) to provide a catalyst-depleted transesterification reaction medium comprising a transesterification reaction product of an alkoxysilane, such separation being achieved by: for example, (i) hydrolyzing the metal transesterification catalyst under conditions effective for hydrolysis, such as a temperature of from about 1 ℃ to about 75 ℃, preferably from about 15 ℃ to about 40 ℃, a pressure of from about 0.01 bar to about 2 bar, preferably from about 0.5 bar to about 1.2 bar, and an amount of water of from about 0.1 to about 10 weight percent, preferably from about 0.2 to about 8 weight percent, based on the weight of the alkoxysilane-based transesterification product, to provide a metal oxide-containing hydrolysate which is then removed from the transesterification reaction medium, for example by filtration or decantation, or (ii) adsorbing the metal transesterification catalyst on an adsorption medium followed by removing the adsorption medium containing the transesterification catalyst from the transesterification reaction medium, for example by filtration or decantation; and optionally (c) a second set of instructions,
(f) separating the transesterification reaction product of the alkoxysilane from the transesterification reaction medium depleted in the transesterification catalyst of step (e), for example by distillation.
The following examples are illustrative of the process of the present invention.
Example 1
Preparation of 3-glycidoxypropyltriethoxysilane
This example illustrates the transesterification reaction product of 3-glycidoxypropyltriethoxysilane using titanium isopropoxide (TPT) as the metal-containing transesterification catalyst.
A5-liter flask equipped with a mechanical stirrer, heating mantle, temperature probe connected to a temperature controller, short path distillation head, and maintained under nitrogen blanket (blanket) was charged with 3-glycidoxypropyltrimethoxysilane (2587.0 g, 10.95 moles) and TPT catalyst (31.5 g, 0.11 moles). The mixture was stirred at 290rpm, the temperature was set at 100 ℃ and the pressure was about 1 bar. Once the temperature was reached, the addition of ethanol (6783.4 g, 147.25 moles) was started. Ethanol was added to the reactor by means of a piston pump over about 12 hours, the feed rate being adjusted to the desired value. During the addition of ethanol, by-product methanol and excess ethanol were removed using a short path distillation procedure. The amount of crude product formed was 3295.0 grams and the amount of titanium was 1611 ppm.
After the transesterification reaction reaches the desired conversion (conversion), the crude reaction mixture is allowed to cool to ambient temperature. Then, about 5 weight percent of demineralized water was added to the crude 3-glycidoxypropyltriethoxysilane and stirred for 1.5-2 hours. After the addition of water, the appearance of the crude reaction mixture changed immediately from a yellow clear liquid to a white turbid solution due to hydrolysis of TPT and precipitation of titanium oxide hydrolysate.
About 1 weight percent of filter aid diatomaceous earth was added to the reactor prior to filtration. After filtration through a 1 μm pore size PTFE membrane (5 bar pressure), the crude product was light yellow in appearance and clear.
The crude product is then distilled in a batch distillation. The material was charged to a 5-liter round bottom flask equipped with a heating mantle, a temperature probe connected to a temperature controller, a magnetic stirrer and stirrer bar, a short path distillation head with multiple receivers, and cold hydrazine. The distillation conditions were: 6mmHg, 138 ℃ and overhead (overhead). The lights were predominantly water and ethanol, while the heavies were predominantly siloxane and 213ppm Ti. The distilled material was light yellow in appearance and clear. The purity by GC was 97.0 percent and the amount of titanium metal was less than 10ppm titanium. These data are shown in table 1, along with the crude product and the loading (charge) prior to hydrolysis.
Example 2
Preparation of 3-glycidoxypropyltriethoxysilane
This example was carried out under conditions similar to those of example 1 except that the loading was slightly different. The amount of glycidoxypropyltrimethoxysilane was 3512.5 grams, TPT was 40.0 grams, and ethanol was 9500.8 grams. The amount of crude product formed was 4496.9 grams and the amount of titanium was 1499 ppm.
Purity by GC was 97.2 percent and less than 10ppm titanium. These data are listed in table 1 below, along with the crude product and loading prior to hydrolysis.
Example 3
Removal of TPT from transesterification media of 3-glycidoxypropyltriethoxysilane by hydrolysis and filtration
This example demonstrates the effectiveness of hydrolysis and filtration for removing TPT from a transesterification reaction medium and subsequent distillation for recovering a 3-glycidoxypropyltriethoxysilane reaction product from a TPT-depleted reaction medium.
A0.5-liter flask equipped with a mechanical stirrer, heating mantle, temperature probe connected to a temperature controller, short path distillation head, and under nitrogen blanket was charged with 3-glycidoxypropyltrimethoxysilane (264.9 g, 1.12 moles) and TPT (3.2 g, 0.01 moles). The mixture was stirred at 290RPM and the temperature was set to 100 ℃ and about 1 bar. Once the temperature was reached, the addition of ethanol (577.8 g, 12.5 moles) was started. Ethanol was added to the reactor by means of a piston pump and the feed rate was adjusted to the desired value just before the experiment. The addition of ethanol took about 11 hours. During the addition of ethanol, a short path distillation process is used to remove the by-product methanol and excess ethanol. The amount of crude product formed was 338.10 grams and the amount of titanium was 2445 ppm.
Once the reaction reaches the desired conversion, the crude reaction mixture is allowed to cool to ambient temperature. Then, about 2 weight percent of demineralized water was added to the crude 3-glycidoxypropyltriethoxysilane and held under agitation for 1.5-2 hours. Immediately after the addition of water, the appearance of the crude reaction mixture changed from a yellow clear liquid to a white turbid solution due to hydrolysis of TPT and precipitation of titanium oxide. About 1% of filter aid was added to the reactor prior to filtration. After filtration through a 1 μm pore size PTFE membrane (5 bar pressure), the crude reaction product was light yellow in appearance and clear.
The crude reaction product is then distilled in a batch distillation. The material was charged to a 0.5 liter round bottom flask equipped with a heating mantle, a temperature probe connected to a temperature controller, a magnetic stirrer and stirrer bar, a short path distillation head with multiple receivers, and cold hydrazine. The distillation conditions were: 6mmHg at 138 ℃ and above. The lights were predominantly water and ethanol, while the heavies were predominantly siloxane and 213ppm Ti. The distilled material was light yellow in appearance and clear. The purity by GC was 95.9 percent and the amount of titanium metal was less than 3.5ppm titanium. These data are shown in Table 1, along with the crude product and loading prior to hydrolysis.
Comparative example 1
Preparation and recovery of 3-glycidoxypropyltriethoxysilane without prior removal of TPT
This comparative example shows that TPT can contaminate the transesterified reaction product of distilled 3-glycidoxypropyltriethoxysilane unless at least a substantial amount (e.g., at least 90 weight percent, more preferably at least 95 weight percent, and more preferably at least 99 weight percent) of the TPT is removed prior to recovering the reaction product from the transesterified reaction medium.
A1-liter flask equipped with a mechanical stirrer, heating mantle, temperature probe connected to a temperature controller, short path distillation head, and nitrogen source was charged with 3-glycidoxypropyltrimethoxysilane (300.2 g, 1.27 moles) and TPT (3.7 g, 0.013 moles). The mixture was stirred at 290rpm, the temperature was set to 100 ℃ and the pressure was about 1 bar. Once the temperature was reached, the addition of ethanol (552.3 g, 12.0 moles) was started. Ethanol was added to the reactor by means of a piston pump and the feed rate was adjusted to the desired value just before the run. The addition of ethanol took about 11 hours. The amount of crude product formed was 339.8 grams and the amount of titanium was 2049 ppm.
The crude reaction product is then distilled in a batch distillation. The material was charged to a 1-liter round bottom flask equipped with a heating mantle, a temperature probe connected to a temperature controller, a magnetic stirrer and stir bar, a 10-tray Oldershaw distillation column, a variable reflux distillation head with multiple receivers, and cold hydrazine. The distillation conditions were: 6mmHg at 138 ℃ and above. The light materials are mainly methanol and ethanol, and the heavy materials are mainly siloxane. The distilled material was a clear liquid as well as a dispersed white solid. TPT is co-distilled with 3-glycidoxypropyltriethoxysilane, and the use of a 10 tray column and a reflux ratio of about 10 does not separate the two materials. As a result, TPT severely contaminates distilled 3-glycidoxypropyltriethoxysilane. TPT (melting point 15-17 ℃) crystallizes on cooling in the distillation head, which in turn leads to blockages in the apparatus.
Table 1 below lists the reactants, catalyst loading and composition of the transesterification reaction product before and after catalyst removal and distillation for examples 1-3 and comparative example 1:
TABLE 1
This value is relative to the liquid phase only. Excluding the white solids present in the sample.
Example 4
Removal of TPT from transesterification media of 3-glycidoxypropyltriethoxysilane by adsorption
This example illustrates the adsorption procedure used to remove the metal transesterification catalyst from a transesterification reaction medium containing 3-glycidoxypropyltriethoxysilane.
A0.5-liter flask equipped with a mechanical stirrer, heating mantle, temperature probe connected to a temperature controller, short path distillation head, and nitrogen source was charged with 3-glycidoxypropyltrimethoxysilane and TPT. The mixture was stirred and the temperature was set to 100 ℃. Once the temperature was reached, the addition of ethanol was started. Ethanol was added to the reactor by means of a piston pump over about 12 hours and the feed rate was adjusted to the desired value. The amounts of the reactants were similar to those of example 3.
After the reaction reached the desired conversion, 8 grams of precipitated silica was added to the crude reaction mixture and stirred at 100 ℃ for 1 hour. The reaction mixture was then cooled and filtered to remove solids. The resulting product, 3-glycidoxypropyltriethoxysilane, contains less than 100ppm Ti, as measured by ICP.
While the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (32)
1. A process for preparing a transesterification reaction product of an alkoxysilane having the general formula (IV):
Y-[R1-Si(R2)3-a(OR3)a-c(OR4)c]b (IV)
wherein:
y is a functional group selected from glycidyloxy and epoxycyclohexyl;
each R1Independently is a divalent straight chain alkylene group of 1 to 12 carbon atoms, a branched chain alkylene group of 2 to 12 carbon atoms, a cycloalkylene group of 3 to 12 carbon atoms, an arylene group of 6 to 10 carbon atoms, an aromatic group of 7 to 16 carbon atomsAlkyl, alkenylene of 2 to 12 carbon atoms, cycloalkenylene of 3 to 12 carbon atoms, alkynylene of 2 to 12 carbon atoms, linear alkylene, branched alkylene or cycloalkylene comprising at least one heteroatom selected from sulfur, oxygen or nitrogen and 2 to 12 carbon atoms, or a chemical bond, with the proviso that at R1In the case of a chemical bond, the silicon atom is bonded to a carbon atom of the group Y;
each R2Independently a monovalent straight chain alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 16 carbon atoms;
each R3Independently a monovalent straight chain alkyl of 1 to 4 carbon atoms or a branched alkyl of 3 to 4 carbon atoms;
each R4Is a monovalent linear alkyl of 1 to 16 carbon atoms, a branched alkyl of 3 to 16 carbon atoms, a cycloalkyl of 3 to 12 carbon atoms, an alkenyl of 2 to 16 carbon atoms, an aralkyl of 7 to 12 carbon atoms, an aryl of 6 to 10 carbon atoms, a linear alkyl containing 2 to 16 carbon atoms containing at least one heteroatom selected from oxygen, sulfur or nitrogen or a branched alkyl containing 3 to 16 carbon atoms containing at least one heteroatom selected from oxygen, sulfur or nitrogen, a linear alkyl of 2 to 16 carbon atoms, a branched alkyl of 2 to 16 carbon atoms and substituted with at least one hydroxyl or amino group-NR5R6Substituted linear or branched alkyl, wherein R5And R6Independently hydrogen or a straight chain alkyl group of 1 to 16 carbon atoms, a branched alkyl group of 3 to 16 carbon atoms, an aryl group of 6 to 10 carbon atoms or an aralkyl group of 7 to 12 carbon atoms
a is an integer of 2 to 3;
b is 1; and
c is an integer of 1 to 3;
provided that a and b are the values selected for the transesterifiable alkoxysilane (I) and c is selected such that a-c are 0 or positive integers,
the process comprises transesterifying at least one transesterifiable alkoxysilane and at least one transesterified alcohol under transesterification reaction conditions in the presence of at least one metal transesterification catalyst with concomitant removal of by-product alcohol to produce a crude transesterified reaction product of the alkoxysilane; subsequently, removing at least a portion of the metal transesterification catalyst from the crude alkoxysilane transesterification reaction product by either (i) a process comprising: (iii) hydrolyzing the metal transesterification catalyst to form a metal oxide precipitate, and then followed by filtration to remove the metal oxide precipitate from the crude alkoxysilane transesterification reaction product, said process (ii) comprising: adsorbing the metal transesterification catalyst onto an adsorption medium and then filtering the adsorption medium containing the adsorbed transesterification catalyst,
wherein the metal transesterification catalyst is of the general formula (III):
Mn+(X)n (III)
wherein:
m is Ti or Zr;
x is OR7Wherein each R is7Independently a monovalent straight chain alkyl of 1 to 12 carbon atoms, OR a branched alkyl of 3 to 12 carbon atoms, OR two OR' s7The radicals being bonded to one another via carbon-carbon bonds to form-O-R7-R7-an O-group; and the combination of (a) and (b),
n is the valence of M.
2. The process of claim 1, wherein the transesterifiable alkoxysilane is a transesterifiable alkoxysilane of the general formula (I):
Y-[R1-Si(R2)3-a(OR3)a]b (I)
wherein:
y is a functional group selected from glycidyloxy and epoxycyclohexyl;
each R1Independently is a divalent straight chain alkylene group of 1 to 12 carbon atoms, a branched chain alkylene group of 2 to 12 carbon atoms, a cycloalkylene group of 3 to 12 carbon atoms, an arylene group of 6 to 10 carbon atoms, an aralkyl group of 7 to 16 carbon atoms, an alkylene group of 2 to 12 carbon atoms, a cycloalkylene group of 3 to 12 carbon atoms, a 2 to 12 carbon atomA sub-alkynylene group containing at least one heteroatom selected from sulfur, oxygen or nitrogen and a linear, branched or cyclic alkylene group of 2 to 12 carbon atoms, or a chemical bond, with the proviso that at R1In the case of a chemical bond, Y is an organic functional group, silicon being bonded to the carbon of the group Y;
each R2Independently a monovalent straight chain alkyl group containing 1 to 16 carbon atoms, a branched alkyl group containing 3 to 16 carbon atoms, a cycloalkyl group containing 3 to 12 carbon atoms, an aryl group containing 6 to 10 carbon atoms, an aralkyl group containing 7 to 16 carbon atoms;
each R3Independently a monovalent straight chain alkyl of 1 to 4 carbon atoms or a branched alkyl of 3 to 4 carbon atoms;
a is an integer of 2 to 3; and the combination of (a) and (b),
b is 1.
3. The method of claim 2, wherein Y is glycidyloxy.
4. The method of claim 2, wherein-OR3Selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.
5. The method of claim 4, wherein-OR3Is methoxy.
6. The method of claim 2, wherein the integer a is 3.
7. The method of claim 1, wherein the integer c is 3.
8. The process of claim 2, wherein the transesterifiable alkoxysilane (I) is at least one member selected from the group consisting of glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and (3, 4-epoxycyclohexyl) ethyltriethoxysilane.
9. The process of claim 1, wherein the transesterified alcohol is of formula (II):
R4OH (II)
wherein:
R4is a monovalent linear alkyl of 1 to 16 carbon atoms, a branched alkyl of 3 to 16 carbon atoms, a cycloalkyl of 3 to 12 carbon atoms, an alkenyl of 2 to 16 carbon atoms, an aralkyl of 7 to 12 carbon atoms, an aryl of 6 to 10 carbon atoms, a linear alkyl containing 2 to 16 carbon atoms comprising at least one heteroatom selected from oxygen, sulfur or nitrogen, or a branched alkyl containing 3 to 16 carbon atoms comprising at least one heteroatom selected from oxygen, sulfur or nitrogen, a branched alkyl of 2 to 16 carbon atoms and substituted with at least one hydroxyl or amino group-NR5R6Substituted linear or branched alkyl, wherein R5And R6Independently hydrogen, or a straight chain alkyl group of 1 to 16 carbon atoms, a branched alkyl group of 3 to 16 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an aralkyl group of 7 to 12 carbon atoms.
10. The method of claim 9, wherein the transesterified alcohol is at least one member selected from the group consisting of ethanol, propanol, isopropanol, and butanol.
11. The method of claim 1, wherein each R is7Independently a monovalent straight chain alkyl of 1 to 12 carbon atoms or a branched alkyl of 3 to 12 carbon atoms.
12. The method of claim 1, wherein M is Ti.
13. The method of claim 11, wherein the metal transesterification catalyst is at least one member selected from the group consisting of tetraisopropyl titanate, tetraethyl zirconate, and tetrapropyl zirconate.
14. The method of claim 11, wherein the metal transesterification catalyst is 0.01 weight percent to 5 weight percent based on the total weight of the transesterifiable alkoxysilane.
15. The method of claim 14, wherein the metal transesterification catalyst is 0.5 weight percent to 2 weight percent based on the total weight of the transesterifiable alkoxysilane.
16. The process of claim 1, wherein the conditions of the transesterification reaction include a temperature from room temperature to 120 ℃ and a pressure from 0.0007 bar to 2 bar.
17. The process of claim 16, wherein the conditions of the transesterification reaction include a temperature from 50 ℃ to 100 ℃ and a pressure from 0.02 bar to 1 bar.
18. The process of claim 1 wherein the residual level of metal in the transesterification reaction product of the alkoxysilane after removal of the metal transesterification catalyst is less than 100ppm based on the weight of the transesterification reaction product of the alkoxysilane.
19. The process of claim 18, wherein the residual level of metal in the transesterification reaction product of the alkoxysilane after removal of the metal transesterification catalyst is less than 50 ppm.
20. The process of claim 19 wherein the residual level of metal in the transesterification reaction product of the alkoxysilane after removal of the metal transesterification catalyst is less than 10 ppm.
21. The process of claim 1 wherein hydrolyzing the metal transesterification catalyst comprises adding sufficient water in an amount of 0.1 to 10 weight percent based on the weight of the alkoxysilane based transesterification reaction product to completely hydrolyze the metal transesterification catalyst and form the catalyst metal oxide.
22. The process of claim 21, wherein hydrolyzing the metal transesterification catalyst comprises hydrolysis conditions of a temperature from 1 ℃ to 75 ℃ and a pressure from 0.0007 bar to 2 bar.
23. The method of claim 1, wherein removing the catalyst metal oxide comprises filtering.
24. The process of claim 1, further comprising purifying the transesterification reaction product of the alkoxysilane by distillation.
25. The method of claim 1, further comprising adding an acid to the transesterification reaction product of the alkoxysilane.
26. The method of claim 25, wherein the acid is acetic acid.
27. The method of claim 25, wherein the acid is boric acid.
28. The process of claim 1 wherein the catalyst is removed by adsorption on an adsorption media selected from the group consisting of fumed silica, precipitated silica, clays, and ion exchange resins.
29. The method of claim 28, wherein the adsorbent media is precipitated silica.
30. The process for preparing a transesterification reaction product of an alkoxysilane according to claim 1, further comprising:
(a) combining the metal transesterification catalyst and the transesterifiable alkoxysilane in an amount of 0.005 to 5 weight percent, based on the weight of the transesterifiable alkoxysilane, to provide a mixture thereof;
(b) subjecting the mixture from step (a) to transesterification reaction conditions of temperature from room temperature to 120 ℃ and pressure from 0.02 bar to 1 bar while adding transesterified alcohol thereto;
(c) adding a transesterification alcohol to the mixture of step a before and/or during step (b) to provide a transesterification reaction medium to initiate transesterification and to produce a transesterification reaction product of the alkoxysilane once so;
(d) removing from the transesterification reaction medium by-product alcohol formed during transesterification;
(e) separating the metal transesterification catalyst from the transesterification reaction medium of step (d) to provide a catalyst-depleted transesterification reaction medium comprising a transesterification reaction product of an alkoxysilane by: hydrolyzing a metal transesterification catalyst at a temperature of 15 ℃ to 40 ℃ and a pressure of 0.5 bar to 1.2 bar and under conditions effective for hydrolysis in the presence of 0.2 to 8 weight percent water based on the weight of the alkoxysilane based transesterification reaction product to provide the metal oxide precipitate, which is a metal oxide containing hydrolysate, and removing the metal oxide precipitate containing hydrolysate; and, optionally
(f) Separating the transesterification reaction product of the alkoxysilane from the transesterification reaction medium depleted in the transesterification catalyst of step (e).
31. The process of claim 30 wherein in step (e) the metal oxide-containing hydrolyzate is removed from the transesterification reaction medium via filtration or decantation to provide a transesterification medium depleted in transesterification catalyst.
32. The process of claim 31 wherein the transesterification product of the alkoxysilane is recovered from the transesterification reaction medium depleted in the transesterification catalyst by distillation.
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Dendrimeric silatrane wedges;Tim Kemmitt et al.,;《J.Chem.Soc.Perkin Trans.》;19971231;第1卷;第729-739页 * |
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JP2019517554A (en) | 2019-06-24 |
WO2017214252A1 (en) | 2017-12-14 |
EP3468980A1 (en) | 2019-04-17 |
JP7016816B2 (en) | 2022-02-07 |
US20170355720A1 (en) | 2017-12-14 |
US10294251B2 (en) | 2019-05-21 |
CN109311917A (en) | 2019-02-05 |
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